High purity metallic top coat for semiconductor manufacturing components

ABSTRACT

An article comprises a component for a manufacturing chamber, a coating on the component, and an anodization layer formed on the coating. The anodization layer has a thickness of about 2-10 mil, comprises a low porosity layer portion having a density of greater than 99% and a porous columnar layer portion having a higher porosity than the low porosity layer portion. The porous columnar layer portion comprises a plurality of columnar nanopores having a diameter of about 10-50 nm.

RELATED APPLICATIONS

This present application is a continuation of U.S. patent applicationSer. No. 15/847,240, filed Dec. 19, 2017, which is a continuation ofU.S. patent application Ser. No. 15/595,888, filed May 15, 2017, whichis a divisional of U.S. patent application Ser. No. 14/079,586, filedNov. 13, 2013, all of which are herein incorporated by reference.

TECHNICAL FIELD

Embodiments of the present disclosure relate, in general, to metalliccoatings on semiconductor manufacturing components and to a process forapplying a metallic coating to a substrate.

BACKGROUND

In the semiconductor industry, devices are fabricated by a number ofmanufacturing processes producing structures of an ever-decreasing size.Some manufacturing processes such as plasma etch and plasma cleanprocesses expose a substrate to a high-speed stream of plasma to etch orclean the substrate. The plasma may be highly corrosive, and may corrodeprocessing chambers and other surfaces that are exposed to the plasma.This corrosion may generate particles, which frequently contaminate thesubstrate that is being processed, contributing to device defects (i.e.,on-wafer defects, such as particles and metal contamination).

As device geometries shrink, susceptibility to defects increases andallowable levels of particle contamination may be reduced. To minimizeparticle contamination introduced by plasma etch and/or plasma cleanprocesses, chamber materials have been developed that are resistant toplasmas. Different materials provide different material properties, suchas plasma resistance, rigidity, flexural strength, thermal shockresistance, and so on. Also, different materials have different materialcosts. Accordingly, some materials have superior plasma resistance,other materials have lower costs, and still other materials havesuperior flexural strength and/or thermal shock resistance.

SUMMARY

In one embodiment, a method includes providing a component for amanufacturing chamber, loading the component into a deposition chamber,cold spray coating a metal powder on the component to form a coating onthe component, and anodizing the coating to form an anodization layer.

The method can also include polishing the component such that an averagesurface roughness of the component is less than about 20 micro-inchesprior to anodizing the coating. The metal powder being cold spray coatedon to the component can have a velocity in a range from about 100 m/s toabout 1500 m/s. The powder can be sprayed via a carrier gas of Nitrogenor Argon.

The method can include heating the component after cold spray coating toa temperature in a range from about 200 degrees C. to about 1450 degreesC. for more than about 30 minutes to form a barrier layer between thecomponent and the coating.

The coating can have a thickness in a range from about 0.1 mm to about40 mm. The component can include Aluminum, an Aluminum alloy, stainlesssteel, Titanium, a Titanium alloy, Magnesium, or a Magnesium alloy. Themetal powder can include Aluminum, an Aluminum alloy, Titanium, aTitanium alloy, Niobium, a Niobium alloy, Zirconium, a Zirconium alloy,Copper, or a Copper alloy.

About 1 to about 50 percent of the coating can be anodized to form theanodization layer. The component can be a showerhead, a cathode sleeve,a sleeve liner door, a cathode base, a chamber line, or an electrostaticchuck base.

In one embodiment an article includes a component for a manufacturingchamber for plasma etching, a metal coating on the component, and ananodization layer formed of the coating.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure is illustrated by way of example, and not by wayof limitation, in the figures of the accompanying drawings in which likereferences indicate similar elements. It should be noted that differentreferences to “an” or “one” embodiment in this disclosure are notnecessarily to the same embodiment, and such references mean at leastone.

FIG. 1 illustrates a coating on a substrate, in accordance with oneembodiment of the present invention;

FIG. 2 an exemplary architecture of a manufacturing system, inaccordance with one embodiment of the present invention;

FIG. 3 illustrates a process of applying a coating to a substrate, inaccordance with one embodiment of the present invention;

FIG. 4 illustrates a process of anodizing a coating on a substrate, inaccordance with one embodiment of the present invention; and

FIG. 5 illustrates a method of forming a coating on a substrate, inaccordance with one embodiment of the present invention.

DETAILED DESCRIPTION OF EMBODIMENTS

Embodiments of the disclosure are directed to a process for applying acoating to a substrate, such as a component for use in a semiconductormanufacturing chamber. A component for use in a semiconductormanufacturing chamber can be cold spray coated with a metal powder toform a coating on the component, and the coating can be anodized to forman anodization layer. Cold spray coating of metal powders can provide adense and conforming coating that has increased resistance to aggressiveplasma chemistries. The coating can be formed of high purity materialsto reduce the metal contamination level inside the chamber. A coatingwith an anodization layer can increase the lifetime of the component anddecrease on-wafer defects during semiconductor manufacturing because itis erosion resistant. Therefore, levels of particle contamination can bereduced.

The component that is cold spray coated can be formed of Aluminum, anAluminum alloy, stainless steel, Titanium, a Titanium alloy, Magnesium,or a Magnesium alloy. The component can be a showerhead, a cathodesleeve, a sleeve liner door, a cathode base, a chamber line, anelectrostatic chuck base, or another component of a processing chamber.Also, the component can be polished to lower an average surfaceroughness prior to anodizing the coating. Additionally, the componentcan be heated after cold spray coating of the coating to form a barrierlayer between the component and the coating.

The metal powder being cold spray coated on to the component can have avelocity in a range from about 100 m/s to about 1500 m/s and can besprayed via a carrier gas of Nitrogen or Argon. The coating can have athickness in a range from about 0.1 mm to about 40 mm. The metal powdercan be Aluminum, an Aluminum alloy, Titanium, a Titanium alloy, Niobium,a Niobium alloy, Zirconium, a Zirconium alloy, Copper, or a Copperalloy. About 1-to-50 percent of the coating can be anodized to form theanodization layer.

When the terms “about” and “approximately” are used herein, these areintended to mean that the nominal value presented is precise within±10%. Note also that some embodiments are described herein withreference to components used in plasma etchers for semiconductormanufacturing. However, it should be understood that such plasma etchersmay also be used to manufacture micro-electro-mechanical systems (MEMS)devices.

FIG. 1 illustrates a component 100 with a coating according to oneembodiment. Component 100 includes a substrate 102 with a cold spraycoating 104 and an anodization layer 108. In one embodiment, thesubstrate 102 can be a component for use in a semiconductormanufacturing chamber, such as a showerhead, a cathode sleeve, a sleeveliner door, a cathode base, a chamber liner, an electrostatic chuckbase, etc. For example, the substrate 102 can be formed from Aluminum,Aluminum alloys (e.g., Al 6061, Al 5058, etc.), stainless steel,Titanium, Titanium alloys, Magnesium, and Magnesium alloys. The chambercomponent 100 shown is for representational purposes and is notnecessarily to scale.

In one embodiment, the average surface roughness of the substrate 102 isadjusted prior to the formation of the cold spray coating 104. Forexample, an average surface roughness of the substrate 102 may be in arange from about 15 micro-inches to about 300 micro-inches. In oneembodiment, the substrate has an average surface roughness that startsat or that is adjusted to about 120 micro-inches. The average surfaceroughness may be increased (e.g., by bead blasting or grinding), or maybe decreased (e.g., by sanding or polishing). However, the averagesurface roughness of the article may already be suitable for cold spraycoating. Accordingly, average surface roughness adjustment can beoptional.

The cold spray coating 104 can be formed via a cold spray process. Inone embodiment, the cold spray coating can be formed from a metalpowder, such as Aluminum (e.g., high purity Aluminum), an Aluminumalloy, Titanium, a Titanium alloy, Niobium, a Niobium alloy, Zirconium,a Zirconium alloy, Copper, or Copper alloys. For example, the cold spraycoating 104 can have a thickness in a range from about 0.1 mm to about40 mm. In one example, the thickness of the cold spray coating is about1 mm. The cold spray process will be described in more detail below.

In one embodiment, the component 100 can be thermally treated after theapplication of cold spray coating 104. The thermal treatment canoptimize the cold spray coating by improving bonding strength of thecold spray coating 104 to the substrate 102 by a forming a reaction zone106 between the cold spray coating 104 and the substrate 102.

Subsequently, an anodization layer 108 can be formed from the cold spraylayer 104 via an anodization process to seal and protect the cold spraycoating 104. In the example where the cold spray coating 104 is formedfrom Aluminum, the anodization layer 108 can be formed from Al₂O₃. Theanodization layer 108 can have a thickness in a range from about 2 milto about 10 mil. In one embodiment, the anodization process is an oxalicor hard anodization process. In one example, the anodization processanodizes between about 20% and about 100% of the cold spray coating 102to form the anodization layer 108. In one embodiment, about 50% of thecold spray coating 102 is anodized. The anodization process will bedescribed in more detail below.

Further, the cold spray coating 104 can have a relatively high averagesurface roughness after formation (e.g., having an average surfaceroughness of about 200 micro-inches). In one embodiment, the averagesurface roughness of the cold spray coating 104 is altered prior toanodization. For example, the surface of the cold spray coating 104 canbe smoothed by chemical mechanical polishing (CMP) or mechanicalpolishing or other suitable methods. In one example, the average surfaceroughness of the cold spray coating 104 is altered to have a roughnessin a range from about 2-20 micro-inches).

FIG. 2 illustrates an exemplary architecture of a manufacturing system200 for manufacturing a chamber component (e.g., component 100 of FIG.1). The manufacturing system 200 may be a system for manufacturing anarticle for use in semiconductor manufacturing, such as a showerhead, acathode sleeve, a sleeve liner door, a cathode base, a chamber line, oran electrostatic chuck base. In one embodiment, the manufacturing system200 includes manufacturing machines 201 (e.g., processing equipment)connected to an equipment automation layer 215. The processing equipment201 may include a cold spray coater 203, a heater 204 and/or an anodizer205. The manufacturing system 200 may further include one or morecomputing devices 220 connected to the equipment automation layer 215.In alternative embodiments, the manufacturing system 200 may includemore or fewer components. For example, the manufacturing system 200 mayinclude manually operated (e.g., off-line) processing equipment 201without the equipment automation layer 215 or the computing device 220.

In one embodiment, a wet cleaner cleans the article using a wet cleanprocess where the article is immersed in a wet bath (e.g., after averagesurface roughness adjustment or prior to coatings or layers beingformed). In other embodiments, alternative types of cleaners such as drycleaners may be used to clean the articles. Dry cleaners may cleanarticles by applying heat, by applying gas, by applying plasma, and soforth.

Cold spray coater 203 is a system configured to apply a metal coating tothe surface of the article. For example, the metal coating can be formedof a metal powder of a metal, such as Aluminum, an Aluminum alloy,Titanium, a Titanium alloy, Niobium, a Niobium alloy, Zirconium, aZirconium alloy, Copper, or a Copper alloy. In one embodiment, coldspray coater 203 forms an Aluminum coating on the article by a coldspray process where an Aluminum powder is propelled from a nozzle ontothe article at a high rate of speed, which will be described in moredetail below. Here, surfaces of the article can be coated evenly becausethe article and/or the nozzle of the cold spray coater 203 can bemanipulated to achieve an even coating. In one embodiment, the coldspray coater 203 can have a fixture with a chuck to hold the articleduring coating. The formation of the cold spray coating will bedescribed in more detail below.

In one embodiment, the article can be baked (or thermally treated) in aheater 204 for certain period after the cold spray coating is formed.The heater 204 may be a gas or electric furnace. For example, thearticle may be thermally treated for 0.5 hours to 12 hours at atemperature between about 60 degrees C. to about 1500 degrees C.,depending on the coating and substrate materials. This thermal treatmentmay form a reaction zone or barrier layer between the cold spray coatingand the article, which can improve bonding of the cold spray coating tothe article.

In one embodiment, anodizer 205 is a system configured to form ananodization layer from the cold spray coating. Anodizer 205 may includea current supplier, an anodization bath, and a cathode body. Forexample, the article, which may be a conductive article, is immersed inthe anodization bath. The anodization bath may include sulfuric acid oroxalic acid. An electrical current is applied to the article such thatthe article acts as an anode and the cathode body acts as a cathode. Theanodization layer then forms on the cold spray coating on the article,which will be described in more detail below.

The equipment automation layer 215 may interconnect some or all of themanufacturing machines 201 with computing devices 220, with othermanufacturing machines, with metrology tools and/or other devices. Theequipment automation layer 215 may include a network (e.g., a locationarea network (LAN)), routers, gateways, servers, data stores, and so on.Manufacturing machines 201 may connect to the equipment automation layer215 via a SEMI Equipment Communications Standard/Generic Equipment Model(SECS/GEM) interface, via an Ethernet interface, and/or via otherinterfaces. In one embodiment, the equipment automation layer 215enables process data (e.g., data collected by manufacturing machines 201during a process run) to be stored in a data store (not shown). In analternative embodiment, the computing device 220 connects directly toone or more of the manufacturing machines 201.

In one embodiment, some or all manufacturing machines 201 include aprogrammable controller that can load, store and execute processrecipes. The programmable controller may control temperature settings,gas and/or vacuum settings, time settings, etc. of manufacturingmachines 201. The programmable controller may include a main memory(e.g., read-only memory (ROM), flash memory, dynamic random accessmemory (DRAM), static random access memory (SRAM), etc.), and/or asecondary memory (e.g., a data storage device such as a disk drive). Themain memory and/or secondary memory may store instructions forperforming heat treatment processes described herein.

The programmable controller may also include a processing device coupledto the main memory and/or secondary memory (e.g., via a bus) to executethe instructions. The processing device may be a general-purposeprocessing device such as a microprocessor, central processing unit, orthe like. The processing device may also be a special-purpose processingdevice such as an application specific integrated circuit (ASIC), afield programmable gate array (FPGA), a digital signal processor (DSP),network processor, or the like. In one embodiment, programmablecontroller is a programmable logic controller (PLC).

FIG. 3 illustrates an exemplary architecture of a cold spray processmanufacturing system 300 for forming a cold spray coating on an articleor substrate. The manufacturing system 300 includes a deposition chamber302, which can include a stage 304 (or fixture) for mounting a substrate306. In one embodiment, substrate 306 can be substrate 102 of FIG. 1.Air pressure in the deposition chamber 302 can be reduced via a vacuumsystem 308 to avoid oxidation. A powder chamber 310 containing a metalpowder 316, such as Aluminum, an Aluminum alloy, Titanium, a Titaniumalloy, Niobium, a Niobium alloy, Zirconium, a Zirconium alloy, Copper,or a Copper alloy, is coupled to a gas container 312 containing acarrier gas 318 for propelling the metal powder 316. A nozzle 314 fordirecting the metal powder 316 onto the substrate 306 to form the coldspray coating is coupled to the powder chamber 310.

The substrate 306 can be a component used for semiconductormanufacturing. The component may be a component of an etch reactor, or athermal reactor, of a semiconductor processing chamber, and so forth.Examples of components include a showerhead, a cathode sleeve, a sleeveliner door, a cathode base, a chamber liner, an electrostatic chuckbase, etc. The substrate 306 can be formed in part or in whole fromAluminum, Aluminum alloys (e.g., Al 6061, Al 5058, etc.), stainlesssteel, Titanium, Titanium alloys, Magnesium, and Magnesium alloys, orany other conductive material used in a semiconductor manufacturingchamber component.

In one embodiment, the surface of the substrate 306 can be roughened,prior to formation of the cold spray coating, to an average surfaceroughness of less than about 100 micro inches to improve adhesion of thecoating.

The substrate 306 can be mounted on the stage 304 in the depositionchamber 302 during deposition of a coating. The stage 304 can bemoveable stage (e.g., motorized stage) that can be moved in one, two, orthree dimensions, and/or rotated/tilted about in one or more directions.Accordingly, the stage 304 can be moved to different positions tofacilitate coating of the substrate 306 with metal powder 316 beingpropelled from the nozzle 314 in a carrier gas. For example, sinceapplication of the coating via cold spray is a line of sight process,the stage 304 can be moved to coat different portions or sides of thesubstrate 306. If the substrate 306 has different sides that need to becoated or a complicated geometry, the stage 304 can adjust the positionof the substrate 306 with respect to the nozzle 314 so that the wholeassembly can be coated. In other words, the nozzle 314 can beselectively aimed at certain portions of the substrate 306 from variousangles and orientations. In one embodiment, the stage 304 can also havecooling or heating channels to adjust the temperature of the articleduring coating formation.

In one embodiment, the deposition chamber 302 of the manufacturingsystem 300 can be evacuated using the vacuum system 308, such that avacuum is present in the deposition chamber 302. For example, pressurewithin the deposition chamber 302 may be reduced to less than about 0.1mTorr. Providing a vacuum in the deposition chamber 302 can facilitateapplication of the coating. For example, the metal powder 316 beingpropelled from the nozzle encounters less resistance as the metal powder316 travels to the substrate 306 when the deposition chamber 302 isunder a vacuum. Therefore, the metal powder 316 can impact the substrate306 at a higher rate of speed, which facilitates adherence to thesubstrate 306 and formation of the coating and can help to reduce thelevel of the oxidation of the high purity materials like Aluminum.

The gas container 312 holds pressurized carrier gas 318, such asNitrogen or Argon. The pressurized carrier gas 318 travels underpressure from the gas container 312 to the powder chamber 310. As thepressurized carrier gas 318 travels from the powder chamber 310 to thenozzle 314, the carrier gas 318 propels some of the metal powder 316towards the nozzle 314. In one example, the gas pressure can be in arange from about 50 to about 1000 Psi. In one example, the gas pressureis about 500 Psi for Aluminum powder. In another example, the gaspressure is less than about 100 Psi for Tin and Zinc powders.

In one embodiment, a gas temperature is in a range from about 100 toabout 1000 degrees Celsius (C). In another example, a gas temperature isin a range from about 325 to about 500 degrees C. In one embodiment, atemperature of the gas at the nozzle is in a range from about 120 toabout 200 degrees C. The temperature of the metal powder impacting thesubstrate 306 can depend on the gas temperature, travel speed, and thesize of the substrate 306.

In one embodiment, the coating powder 116 has a certain fluidity. In oneexample, the particles can have a diameter in a range from about 1microns to about 200 microns. In one example, the particles can have adiameter in a range from about 1 microns to about 50 microns.

As the carrier gas 318 propelling a suspension of the metal powder 316enters the deposition chamber 302 from an opening in the nozzle 314, themetal powder 316 is propelled towards the substrate 306. In oneembodiment, the carrier gas 318 is pressurized such that the coatingpowder 316 is propelled towards the substrate 306 at a rate of around100 m/s to about 1500 m/s. For example, the coating powder can bepropelled towards the substrate at a rate of around 300 to around 800msec.

In one embodiment, the nozzle 314 is formed to be wear resistant. Due tothe movement of the coating powder 316 through the nozzle 314 at a highvelocity, the nozzle 314 can rapidly wear and degrade. However, thenozzle 314 can be formed in a shape and from a material such that wearis minimized or reduced, and or the nozzle can be made as a consumablepart. In one embodiment, a nozzle diameter can be in a range from about1 millimeter (mm) to about 15 mm. In one example, the nozzle diametercan be in a range from about 3 mm to about 12 mm. For example, thenozzle diameter can be about 6.3 mm for Aluminum powder. In oneembodiment, the nozzle stand-off (i.e., the distance from the nozzle 314to the substrate 306) can be in a range from about 5 mm to about 200 mm.For example, the nozzle stand-off can be in a range from about 10 mm toabout 50 mm.

Upon impacting the substrate 306, the particles of the metal powder 316fracture and deform from the kinetic energy to produce an anchor layerthat adheres to the substrate 306. As the application of the metalpowder 316 continues, the particles become a cold spray coating or filmby bonding to themselves. The cold spray coating on the substrate 306continues to grow by continuous collision of the particles of thecoating powder 316 on the substrate 306. In other words, the particlesare mechanically colliding with each other and the substrate at a highspeed to break into smaller pieces to form a dense layer. Notably, withcold spraying the particles may not melt and reflow.

In one embodiment, the particle crystal structure of the particles ofthe metal powder 316 remains after application to the substrate 306. Inone embodiment, partial melting can happen when kinetic energy convertsto thermal energy due to the particles breaking into smaller pieces uponimpacting the substrate 306. These particles may become densely bonded.As mentioned, the temperature of the metal powder on the substrate 306can depend on the gas temperature, travel speed, and the size (e.g., thethermal mass) of the substrate 306.

In one embodiment, a coating deposition rate can be in a range fromabout 1 to about 50 grams/min. For example, the coating deposition ratecan be in a range from about 1 to about 20 grams/min for Aluminumpowder. Denser coatings can be achieved by a slower feed and fasterraster (i.e., travel speed). In one embodiment, efficiency is in a rangefrom about 10 percent to about 90 percent. For example, efficiency canbe in a range from about 30 percent to about 70 percent. Highertemperature and higher gas pressure can lead to higher efficiency.

In one embodiment, an average surface roughness of the coating may beincreased (e.g., by bead blasting or grinding), or may be decreased(e.g., by sanding or polishing) to achieve an average surface roughnessin a range from about 2 micro-inches to about 300 micro-inches, with asurface roughness of about 120 micro-inches in one particularembodiment. For example, the coating can be bead blasted with Al₂O₃particles with a diameter in a range from about 20 microns to about 300microns. In one example, the particles can have a diameter in a rangefrom about 100 microns to about 150 microns. In one embodiment, betweenabout 10 percent and about 50 percent of the coating may be removedduring adjustment of the average surface roughness. However, the averagesurface roughness of the article may already be suitable, so averagesurface roughness adjustment can be optional.

Unlike application of a coating via plasma spray (which is a thermaltechnique performed at elevated temperatures), application of a coldspray coating via one embodiment can be performed at room-temperature ornear room temperature. For example, application of the cold spraycoating can be performed at around 15 degrees C. to about 100 degreesC., depending on the gas temperature, travel speed, and size of thecomponent. In the case of a cold spray deposition, the substrate may notbe heated and the application process does not significantly increasethe temperature of the substrate being coated.

Furthermore, coatings according to embodiments may have few or no oxideinclusions and low porosity due to solidification shrinkages.

In one embodiment, the cold spray coating can be very dense, e.g.,greater than about 99% density. Further, the cold spray coating can havegood adhesion to the substrate without inter-layers, e.g. about 4,500psi for Aluminum coatings.

Typically, there is little or no thermally-induced difference betweenthe powder and the cold spray coating. In other words, what is in thepowder is in the coating. Also, typically there is little or no damageto the microstructure of the substrate or component during cold spraycoating. Also, the cold spray coating generally exhibits a high hardnessand a cold work microstructure. A high amount of cold work occurs byheavy plastic deformation of the ductile coating materials, whichresults in a very fine grain structure that can be beneficial formechanical and corrosion properties of the coating.

Cold spray coating is generally in the compression mode which helps toreduce delamination of the coating or macro or microscopic cracking inthe coating layer.

In one embodiment, gradient deposits can be used to achieve a compositelayer with desired mechanical and corrosion properties. For example, anAluminum layer is first deposited and a Copper layer is deposited on topof the Aluminum layer.

In one embodiment, the coated substrate 306 can be subjected to apost-coating process. The post cleaning process may be a thermaltreatment, which can further control a coating interface between thecoating and the substrate to improve adhesion and/or create a barrierlayer or reaction zone. In one embodiment, the coated substrate can beheated to a temperature in a range from about 200 degrees C. to about1450 degrees C. for more than about 30 minutes. For example, a Y layercan be heated to about 750 degrees C. to oxidize the surface of the Ylayer to Y₂O₃, thus improving erosion resistance.

In one embodiment, the formation of a barrier layer or reaction zonebetween a coating and a substrate prohibits the reaction of processchemistry that penetrates the coating with an underlying substrate. Thismay minimize the occurrence of delamination. The reaction zone mayincrease adhesion strength of the ceramic coating, and may minimizepeeling. For example, the barrier layer can be an intermetallic compoundor a solid solution region formed between two materials, such an AlTiintermetallic or solid solution between an Al layer and a Ti layer.

The reaction zone grows at a rate that is dependent upon temperature andtime. As temperature and heat treatment duration increase, the thicknessof the reaction zone also increases. Accordingly, the temperature (ortemperatures) and the duration used to heat treat the component shouldbe chosen to form a reaction zone that is not thicker than around 5microns. In one embodiment, the temperature and duration are selected tocause a reaction zone of about 0.1 microns to about 5 microns to beformed. In one embodiment, the reaction zone has a minimum thicknessthat is sufficient to prevent gas from reacting with the ceramicsubstrate during processing (e.g., around 0.1 microns). In oneembodiment, the barrier layer has a target thickness of 1-2 microns.

FIG. 4 illustrates a process 400 for anodizing an article 403 to form ananodization layer 411 from a cold spray coating 409, according to oneembodiment. For example, article 403 can be substrate 102 of FIG. 1.Anodization changes the microscopic texture of the surface of thearticle 403. Accordingly, FIG. 4 is for illustration purposes only andmay not be to scale. Preceding the anodization process, the article 403can be cleaned in a nitric acid bath. The cleaning may performdeoxidation prior to anodization.

The article 403 with cold spray coating 409 is immersed in ananodization bath 401 along with a cathode body 405. The anodization bathmay include an acid solution. Examples of cathode bodies for anodizingan Aluminum coating include Aluminum alloys such as Al6061 and Al3003 aswell as carbon bodies. The anodization layer 411 is grown from the coldspray coating 409 on the article 403 by passing a current through anelectrolytic or acid solution via a current supplier 407, where thearticle 403 is the anode (the positive electrode). The current supplier407 may be a battery or other power supply. The current releaseshydrogen at the cathode body 405 (the negative electrode) and oxygen atthe surface of the cold spray coating 409 to form an anodization layer411 over the cold spray coating 409. The anodization layer is AluminumOxide in the case of an Aluminum cold spray coating 409. In oneembodiment, the voltage that enables anodization using various solutionsmay range from 1 to 300 V. In one embodiment, the voltage ranges from 15to 21 V. The anodizing current varies with the area of the cathode body405 (e.g., aluminum body) anodized, and can range from 30 to 300amperes/meter² (2.8 to 28 ampere/ft²).

The acid solution dissolves (i.e., consumes or converts) a surface ofthe cold spray coating 409 to form a layer of pores (e.g., columnarnanopores). The anodization layer 411 continues growing from this layerof nanopores. The nanopores may have a diameter in a range from about 10nm to about 50 nm. In one embodiment, the nanopores have an averagediameter of about 30 nm.

The acid solution can be oxalic acid, sulfuric acid, a combination ofoxalic acid and sulfuric acid. For oxalic acid, the ratio of consumptionof the article to anodization layer growth is about 1:1. Electrolyteconcentration, acidity, solution temperature, and current are controlledto form a consistent Aluminum oxide anodization layer 411 from coldspray coating 409. In one embodiment, the anodization layer can be grownto have a thickness in a range from about 300 nm to about 200 microns.In one embodiment, the formation of the anodization layer consumes apercentage of the cold spray coating in a range from about 5 percent toabout 100 percent. In one example, the formation of the anodizationlayer consumes about 50 percent of the cold spray coating.

In one embodiment, the current density is initially high (>99%) to growa very dense (>99%) barrier layer portion of the anodization layer, andthen current density is reduced to grow a porous columnar layer portionof the anodization layer. In one embodiment where oxalic acid is used toform the anodization layer, the porosity is in a range from about 40% toabout 50%, and the pores have a diameter in a range from about 10 nm toabout 50 nm.

In one embodiment, the average surface roughness (Ra) of the anodizationlayer is in a range from about 15 micro-inch to about 300 micro-inch,which can be similar to the initial roughness of the article. In oneembodiment, the average surface roughness is about 120 micro-inches.

Table A shows the results of Induction Coupled Plasma Mass Spectroscopy(ICP-MS) used to detect metallic impurities in an Al6061 article and ananodized cold spray high purity Al coating on an Al6061 article. In thisexample, the anodized cold spray high purity Al coating on an Al6061article showed significantly less trace metal contamination than a 6061Al component without a coating.

TABLE A Surface Concentration (×10¹⁰ atoms/cm²) Method Cold SprayDetection 6061 Anodized Anodized Limit Aluminum pure Aluminum Aluminum(Al) 50 81,000 45,000 Antimony (Sb) 0.5 1.7 0.67 Arsenic (As) 5 <5 <5Barium (Ba) 10 <10 <10 Beryllium (Be) 30 <30 <30 Bismuth (Bi) 0.5 <0.5<0.5 Boron (B) 200 550 <200 Cadmium (Cd) 1 <1 <1 Calcium (Ca) 70 1,100<70 Chromium (Cr) 20 43 <20 Cobalt (Co) 5 <5 <5 Copper (Cu) 10 310 190Gallium (Ga) 1 6.1 <1 Germanium (Ge) 10 <10 <10 Iron (Fe) 20 120 270Lead (Pb) 3 <3 22 Lithium (Li) 20 80 <20 Magnesium (Mg) 50 130 <50Manganese (Mn) 5 8.0 <5 Molybdenum (Mo) 2 <2 <2 Nickel (Ni) 10 360 18Potassium (K) 50 250 <50 Sodium (Na) 50 170 51 Strontium (Sr) 5 <5 <5Tin (Sn) 5 <5 <5 Titanium (Ti) 20 72 <20 Tungsten (W) 2 <2 <2 Vanadium(V) 5 7.6 <5 Zinc (Zn) 20 750 120 Zirconium (Zr) 0.5 24 1.2

FIG. 5 is a flow chart showing a method 500 for manufacturing a coatedcomponent, in accordance with embodiments of the present disclosure.Method 500 may be performed using the manufacturing system 200 of FIG.2.

At block 502, a component for use in a semiconductor manufacturingenvironment is provided. For example, the component can be a substrate,as described above, such as a showerhead, a cathode sleeve, a sleeveliner door, a cathode base, a chamber liner, an electrostatic chuckbase, etc. For example, the substrate can be formed from Aluminum,Aluminum alloys (e.g., Al 6061, Al 5058, etc.), stainless steel,Titanium, Titanium alloys, Magnesium, and Magnesium alloys.

At block 504, the component is loaded into a deposition chamber. Thedeposition chamber can be deposition chamber 302 described above.

At block 506, a cold spray coating is coated on the component byspraying a nanoparticle metal powder onto the component, where the coldspray coating can have a thickness in a range from about 0.5 mm to about2 mm. For example, the metal powder can include Aluminum (e.g., highpurity Aluminum), an Aluminum alloy, Titanium, a Titanium alloy,Niobium, a Niobium alloy, Zirconium, a Zirconium alloy, Copper, orCopper alloys. The metal powder may be suspended in a gas such asNitrogen or Argon.

At block 508, the method further includes thermally treating the coatedcomponent to form a reaction zone or barrier layer between the componentand the coating, according to one embodiment. For example, the coatedcomponent can be heated to 1450 degrees C. for more than 30 minutes.

At block 510, the method further includes preparing the surface of thecomponent, according to one embodiment. For example, the cold spraycoating may have an average surface roughness that is not ideal. Thus,the average surface roughness of the cold spray coating can be smoothedto lower the average surface roughness (e.g., by polishing) or roughenedto raise the average surface roughness (e.g., by bead blasting orgrinding).

At block 512, the cold spray coating is anodized to form an anodizationlayer. In an example where the cold spray coating is Aluminum, theanodization layer can be Aluminum Oxide, and the formation of theanodization layer can consume a percentage of the cold spray coating ina range from about 5 percent to about 100 percent.

The preceding description sets forth numerous specific details such asexamples of specific systems, components, methods, and so forth, inorder to provide a good understanding of several embodiments of thepresent disclosure. It will be apparent to one skilled in the art,however, that at least some embodiments of the present disclosure may bepracticed without these specific details. In other instances, well-knowncomponents or methods are not described in detail or are presented insimple block diagram format in order to avoid unnecessarily obscuringthe present disclosure. Thus, the specific details set forth are merelyexemplary. Particular implementations may vary from these exemplarydetails and still be contemplated to be within the scope of the presentdisclosure.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearances of the phrase “in oneembodiment” or “in an embodiment” in various places throughout thisspecification are not necessarily all referring to the same embodiment.In addition, the term “or” is intended to mean an inclusive “or” ratherthan an exclusive “or.”

Although the operations of the methods herein are shown and described ina particular order, the order of the operations of each method may bealtered so that certain operations may be performed in an inverse orderor so that certain operation may be performed, at least in part,concurrently with other operations. In another embodiment, instructionsor sub-operations of distinct operations may be in an intermittentand/or alternating manner.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Many other embodiments will beapparent to those of skill in the art upon reading and understanding theabove description. The scope of the disclosure should, therefore, bedetermined with reference to the appended claims, along with the fullscope of equivalents to which such claims are entitled.

What is claimed is:
 1. An article comprising: a component for amanufacturing chamber; a coating on the component; and an anodizationlayer formed on the coating, the anodization layer having a thickness ofabout 2-10 mil, wherein the anodization layer comprises a low porositylayer portion having a density of greater than 99% and a porous columnarlayer portion having a higher porosity than the low porosity layerportion and comprising a plurality of columnar nanopores having adiameter of about 10-50 nm.
 2. The article of claim 1, wherein thecoating has an average surface roughness of less than about 20micro-inch.
 3. The article of claim 1, wherein the article furthercomprises a barrier layer between the component and the coating.
 4. Thearticle of claim 3, wherein the barrier layer has a thickness in a rangeof about 0.1-5.0 microns.
 5. The article of claim 3, wherein the articlecomprises a first one of Aluminum or Titanium, wherein the coatingcomprises a second one of Aluminum or Titanium, and wherein the barrierlayer comprises a solid solution of Aluminum and Titanium.
 6. Thearticle of claim 1, wherein the component comprises at least one ofAluminum, an Aluminum alloy, stainless steel, Titanium, a Titaniumalloy, Magnesium, or a Magnesium alloy.
 7. The article of claim 1,wherein the coating comprises Aluminum, an Aluminum alloy, Titanium, aTitanium alloy, Niobium, a Niobium alloy, Zirconium, a Zirconium alloy,Copper, or a Copper alloy.
 8. The article of claim 1, wherein the porouscolumnar layer portion has a porosity of about 40-50%.
 9. The article ofclaim 1, wherein the component has an average surface roughness of about120 micro-inches.
 10. The article of claim 1, wherein the coatingcomprises a gradient of a first metal and a second metal.
 11. Thearticle of claim 1, wherein the coating has a thickness of about 0.2-5.0mm.
 12. The article of claim 1, wherein the coating is devoid of oxideinclusions.
 13. The article of claim 1, wherein the component is ashowerhead, a cathode sleeve, a sleeve liner door, a cathode base, achamber line, or an electrostatic chuck base.
 14. An article comprisinga component of a manufacturing chamber, a coating on a surface of thecomponent, and an anodization layer on the coating, the article havingbeen manufactured by a process comprising: depositing a coating onto thesurface of the article; and anodizing the coating to form theanodization layer, the anodization layer having a thickness of about2-10 mil, wherein anodizing the coating comprises: applying a firstcurrent density during a start of the anodizing to form a low porositylayer portion of the anodization layer, the low porosity layer portionhaving a density of greater than about 99%; and applying a secondcurrent density that is lower than the first current density during aremainder of the anodizing to form a porous columnar layer portion ofthe anodization layer, the porous columnar layer portion having a higherporosity than the low porosity layer portion and comprising a pluralityof columnar nanopores having a diameter of about 10-50 nm.
 15. Thearticle of claim 14, wherein the porous columnar layer portion of theanodization layer has a porosity of about 40-50%.
 16. A methodcomprising: cold spray coating a metal powder onto an article to form acoating on the article; and anodizing the coating to form an anodizationlayer having a thickness of about 2-10 mil, wherein anodizing thecoating comprises: applying a first current density during a start ofthe anodizing to form a low porosity layer portion of the anodizationlayer, the low porosity layer portion having a density of greater than99%; and applying a second current density that is lower than the firstcurrent density during a remainder of the anodizing to form a porouscolumnar layer portion of the anodization layer over the low porositylayer portion, the porous columnar layer portion comprising a pluralityof columnar nanopores having a diameter of about 10-50 nm,
 17. Themethod of claim 16, wherein the porous columnar layer portion has aporosity of about 40-50%.
 18. The method of claim 16, furthercomprising: performing chemical mechanical polishing (CMP) of thecoating to cause the coating to have an average surface roughness ofless than about 20 micro-inch prior to anodizing the coating.
 19. Themethod of claim 16, further comprising: forming a barrier layer betweenthe article and the coating by heating the article after the cold spraycoating to a temperature in a range from about 200 degrees C. to about1450 degrees C. for more than about 30 minutes, wherein the barrierlayer has a thickness of about 0.5-5.0 microns.
 20. The method of claim16, wherein the coating comprises a mixture of a first metal and asecond metal, and wherein depositing the coating comprises adjusting apercentage of the first metal and the second metal to cause the coatingto have a gradient of the first metal and the second metal.